An efficient protocol for the palladium-catalyzed direct arene C-H acyloxylation of benzothiadiazole-arene derivatives is reported for the first time. The key strategy is the employment of benzothiadiazole as a modifiable directing group. The highly selective mono- or bis-acyloxylation can be achieved by tuning the reaction conditions, affording various acyloxylated benzothiadiazole derivatives, which could offer a rational tailoring of their electronic properties and be applied in organic electronic and optoelectronic materials. Finally, by diversity-oriented modification of the benzothiadiazole directing group, the acyloxylated products can be readily converted into various valuable functionalized (hetero)biaryls.